Pesticidal compositions

ABSTRACT

Thiazolyl-5-carbonamide derivatives of formula I  nd R1 and R2 are as defined herein, have valuable microbicidal activity. They can be used in the form of compositions for controlling or preventing plant diseases.

This is a division of Ser. No. 853,887, filed Mar. 18, 1992, which is acontinuation of Ser. No. 628,772, filed Dec. 17, 1990, now abandoned.

The present invention relates to novel thiazolyl-5-carbonamidederivatives of formula I below. The invention relates also to thepreparation of those compounds and to agrochemical compositions thatcontain at least one of those compounds as active ingredient. Theinvention relates also to the preparation of the said compositions andto the use of the compounds or the compositions for controllingmicroorganisms, especially plant-destructive microorganisms,particularly fungi.

The compounds according to the invention correspond to the generalformula I and include the acid addition salts and metal salt complexesthereof. ##STR2## In this formula: R₃ is 2-furanyl, 2-thienyl, 3-furanylor 3-thienyl;

R₁ and R₂ are each independently of the other

a) C₃ -C₆ cycloalkyl that is unsubstituted or substituted by methyl ormethylthio,

b) the group --CH₂ --X--R₄, and

c) one of the two substituents R₁ and R₂ may also be hydrogen or C₁ -C₄alkyl, wherein X is oxygen or sulfur, and

R₄ is C₁ -C₄ alkyl that may be unsubstituted or substituted by halogenor, in the case of C₂ -C₄ alkyl, also by C₁ -C₃ alkoxy, or wherein R₄ isC₃ -C₄ alkenyl, C₃ -C₄ alkynyl or a phenyl group or benzyl group ofwhich the aromatic ring is unsubstituted or may be substituted byhalogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, CF₃ or by NO₂.

Depending upon the number of carbon atoms indicated, alkyl by itself oras a constituent of another substituent, such as haloalkyl or alkoxy, isto be understood as being, for example, methyl, ethyl, propyl, butyl,and the isomers isopropyl, isobutyl, tert.-butyl or sec.-butyl. Halogen,also referred to as Hal, is fluorine, chlorine, bromine or iodine.Haloalkyl indicates mono- to per-halogenated radicals, for exampleCHCl₂, CH₂ F, CCl₃, CH₂ Cl, CHF₂, CF₃, CH₂ CH₂ Br, C₂ Cl₅, CH₂ Br,CHBrCl etc. Depending upon the number of carbon atoms indicated,cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl.

The compounds of formula I are oils or solids that are stable at roomtemperature and are distinguished by valuable microbicidal properties.They can be used preventively and curatively in the agricultural sectoror related fields for controlling plant-destructive microorganisms. Thecompounds of formula I according to the invention are, when used in lowconcentrations, distinguished not only by excellent microbicidal,especially fungicidal, activity but also by especially good planttolerability.

The compounds of formula I have an asymmetric carbon atom adjacent tothe nitrile group. They can therefore be cleaved into optical antipodesin customary manner. These antipodes have different microbicidalactions.

The invention relates both to the free compounds of formula I and to theaddition salts thereof with inorganic and organic acids and thecomplexes thereof with metal salts.

Salts according to the invention are especially addition salts withacceptable inorganic or organic acids, for example hydrohalic acids, forexample hydrochloric, hydrobromic or hydriodic acid, sulfuric acid,phosphoric acid, phosphorous acid, nitric acid, or organic acids such asacetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid,glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid,benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonicacid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid,p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or1,2-naphthalenedisulfonic acid.

Metal salt complexes of formula I consist of the underlying organicmolecule and an inorganic or organic metal salt, for example thehalides, nitrates, sulfates, phosphates, acetates, trifluoroacetates,trichloroacetates, propionates, tartrates, sulfonates, salicylates,benzoates etc. of the elements of main group II, such as calcium andmagnesium, and main groups III and IV, such as aluminium, tin or lead,and of subgroups I to VIII, such as chromium, manganese, iron, cobalt,nickel, copper, zinc, etc. Subgroup elements of the 4th period arepreferred. The metals can be present in any of the various valenciesattributed to them. The metal complexes may be mono- or poly-nuclear,that is to say they may contain one or more organic molecule componentsas ligands.

An important group of phytofungicides and insecticides comprises thoseof formula I wherein one of the two substituents R₁ and R₂ is C₃ -C₆cycloalkyl that is unsubstituted or substituted by methyl or methylthio,and the other substituent is

d) cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl,

e) the group --CH₂ --X--R₄ or

f) hydrogen or C₁ -C₄ alkyl, while R₃, X and R₄ are as defined above.

Here and hereinbelow this group is referred to as compound group IA.

Among the compounds of group IA, special mention should be made of thosewherein one of the two substituents R₁ and R₂ is C₃ -C₆ cycloalkyl andthe other is cyclobutyl or cyclopropyl, while R₃ is as defined above(group 1AA), and of those, in turn, those compounds wherein R₁ and R₂are cyclopropyl.

Important compounds are also those of group IA wherein

R₁ is C₃ -C₆ cycloalkyl that is unsubstituted or substituted by methylor methylthio,

R₂ is hydrogen, C₁ -C₄ alkyl or the group --CH₂ --X--R₄,

X is oxygen or sulfur, and

R₄ is C₁ -C₄ alkyl that is unsubstituted or substituted by fluorine or,in the case of C₂ -C₄ alkyl, may also be substituted by C₁ -C₃ alkoxy;or wherein R₄ is allyl, propargyl, phenyl or benzyl, the aromatic ringsof the latter radicals being unsubstituted or substituted by one or twoof the substituents fluorine, chlorine, methyl, ethyl, methoxy and CF₃,

while R₃ is as defined above (group IB).

Those compounds of group IB wherein X is oxygen are preferred (groupIBB).

Important compounds within group IBB are those wherein

R₁ is cyclobutyl, cyclopropyl, methylcyclopropyl ormethylthiocyclopropyl,

R₂ is hydrogen, C₁ -C₄ alkyl or --CH₂ --O--R₄, wherein

R₄ is C₁ -C₄ alkyl that is unsubstituted or substituted by fluorine,methoxy or by ethoxy, or wherein R₄ is allyl, propargyl, phenyl,chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl(=subgroup Ib).

Preferred compounds within group Ib are those wherein

R₁ is cyclopropyl,

R₂ is hydrogen, C₁ -C₄ alkyl or --CH₂ --O--R₄, wherein

R₄ is methyl, ethyl, fluoromethyl, difluoromethyl, trifluoroethyl,allyl, propargyl, phenyl or benzyl, while

R₃ is as defined above (=subgroup Ibb).

Especially preferred compounds within group Ibb are those wherein

R₂ is hydrogen, C₁ -C₃ alkyl, methoxymethyl or ethoxymethyl.

Important compounds are also those of group Ia wherein

R₁ is hydrogen, C₁ -C₄ alkyl or the group --CH₂ --X--R₄,

X is oxygen or sulfur, and

R₄ is C₁ -C₄ alkyl that is unsubstituted or substituted by fluorine or,in the case of C₂ -C₄ alkyl, may also be substituted by C₁ -C₃ alkoxy;or wherein R₄ is allyl, propargyl, phenyl or benzyl, the aromatic tingsof the latter radicals being unsubstituted or substituted by one or twoof the substituents fluorine, chlorine, methyl, ethyl, methoxy and CF₃,while

R₂ is C₃ -C₆ cycloalkyl that is unsubstituted or substituted by methylor methylthio, while R₃ is as defined above (=group IC), especiallythose wherein

X is oxygen (=group ICC).

Within that group ICC, preferred compounds are those wherein

R₁ is hydrogen, C₁ -C₄ alkyl or --CH₂ --O--R₄,

R₂ is cyclobutyl, cyclopropyl, methylcyclopropyl ormethylthiocyclopropyl, and

R₄ is C₁ -C₄ alkyl that is unsubstituted or fluoro-substituted or, inthe case of C₂ -C₄ alkyl, may also be substituted by methoxy or ethoxy;or wherein

R₄ is allyl, propargyl, phenyl, chlorophenyl, fluorophenyl, benzyl,chlorobenzyl or fluorobenzyl, while

R₃ is as defined above (=subgroup Ic).

Especially preferred compounds within subgroup Ic are those wherein

R₂ is cyclopropyl, and

R₄ is methyl, ethyl, fluoromethyl, difluoromethyl, trifluoroethyl,allyl, propargyl, phenyl or benzyl (=subgroup Icc).

Of those compounds, special mention should be made of those wherein

R₁ is hydrogen, C₁ -C₃ alkyl, methoxymethyl or ethoxymethyl.

Important compounds are also those thiazolyl-5-carbonamide derivativesof formula I wherein one of the two substituents R₁ and R₂ is the group--CH₂ --X--R₄ and the other substituent is hydrogen, C₁ -C₄ alkyl or--CH₂ --X--R₄,

X is oxygen or sulfur,

R₃ is as defined above, and

R₄ is C₁ -C₄ alkyl that is unsubstituted or substituted by fluorine or,in the case of C₂ -C₄ alkyl, may also be substituted by C₁ -C₃ alkoxy;or wherein R₄ is allyl, propargyl, phenyl or benzyl, the aromatic ringsof the latter radicals being unsubstituted or substituted by one or twoof the substituents fluorine, chlorine, methyl, ethyl, methoxy and CF₃(=subgroup ID).

Of the compounds of group ID, special mention should be made of thosewherein

R₁ is the group --CH₂ --O--R₄,

R₂ is hydrogen, C₁ -C₄ alkyl or --CH₂ --O--R₄,

R₃ is as defined above, and

R₄ is C₁ -C₄ alkyl that is unsubstituted or substituted by fluorine,methoxy or by ethoxy, or wherein R₄ is allyl, propargyl, phenyl,chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl(subgroup IDD).

Preferred compounds of formula I in subgroup IDD are those wherein

R₄ is methyl, ethyl, fluoromethyl, difluoromethyl, trifluoroethyl,allyl, propargyl, phenyl or benzyl (=subgroup Id).

Especially preferred compounds in the last-mentioned subgroup Id arethose wherein

R₂ is hydrogen or C₁ -C₃ alkyl.

Especially preferred compounds in subgroup Id are also compounds wherein

R₁ and R₂ are each independently of the other methoxymethyl orethoxymethyl.

Among the compounds of group ID, special mention should be made of thosecompounds wherein

R₁ is hydrogen, C₁ -C₄ alkyl or the group --CH₂ --O--R₄,

R₂ is --CH₂ --O--R₄,

R₃ is as defined above and

R₄ is C₁ -C₄ alkyl that is unsubstituted or substituted by fluorine,methoxy or by ethoxy, or wherein R₄ is allyl, propargyl, phenyl,chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl(=subgroup IE).

Preferred compounds of group IE are those wherein

R₄ is methyl, ethyl, fluoromethyl, difluoromethyl, trifluoroethyl,allyl, propargyl, phenyl or benzyl (=subgroup IEE).

Especially preferred compounds of group IEE are those wherein R₁ ishydrogen or C₁ -C₃ alkyl.

Furthermore, an important group of phytofungicides comprises thosecompounds of formula I wherein either

a) R₁ is CH₃, C₂ H₅, n--C₃ H₇, isoC₃ H₇, CH₂ --O--CH₃, CH₂ --O--C₂ H₅ orCH₂ --O--CHF₂ or cyclopropyl, and

R₂ is cyclopropyl, or wherein

b) R₁ is CH₂ --O--CH₃, CH₂ --O--C₂ H₅, CH₂ --O--CHF₂ or cyclopropyl, and

R₂ is C₁ -C₃ alkyl, and

R₃ is as defined above (subgroup Alpha).

Among the compounds of the group Alpha, mention should be made of apreferred subgroup wherein

R₁ is CH₃, C₂ H₅, n--C₃ H₇ or iso--C₃ H₇, and

R₂ is cyclopropyl (subgroup Beta).

Furthermore, among the compounds of the group Alpha, mention should bemade of a further preferred subgroup wherein

R₁ =CH₂ --O--CH₃, CH₂ --O--C₂ H₅ or cyclopropyl and

R₂ =CH₃, C₂ H₅, n--C₃ H₇, iso-C₃ H₇ or cyclopropyl (subgroup Gamma).

Compounds of formula I are obtained by reaction of thethiazolyl-5-carboxylic acid of formula V ##STR3## or an acid halide, anester or an acid anhydride thereof, with an aminoacetonitrile of formulaII ##STR4## in the presence or absence of a condensation agent or anacid acceptor, the substituents R₁, R₂ and R₃ being as defined underformula I.

It is advantageous to use the amine component II in slight excess withrespect to component V (for example up to 2 molar equivalents).

An acid halide is to be understood as being especially a chloride,bromide or iodide, and acid esters are to be understood as being thereadily reactive derivatives of C₁ -C₆ alcohols, for example inter aliamethyl, ethyl, propyl, isopropyl, butyl, tert.-butyl and amyl esters.The reaction of V with II is effected in the absence or preferably inthe presence of a condensation agent or an acid acceptor (protonacceptor).

An acid halide of formula V can also be obtained in situ from thethiazolyl-5-carboxylic acid by reaction thereof with reactant II in thepresence of a thionyl halide, for example SOCl₂, and imidazole. Thisprocess variant is included in the above-mentioned process.

The temperature range for the reaction is from -20° C. to 150° C.,preferably from -5° C. to 80° C.

The proton acceptors used may be, for example, inorganic or organicbases, for example alkali metal or alkaline earth metal compounds, forexample the hydroxides, oxides or carbonates of lithium, sodium,potassium, magnesium, calcium, strontium and barium, or alternativelyhydrides, for example sodium hydride. Organic bases that may bementioned are, for example, tertiary amines, such as triethylamine,triethylenediamine, pyridine and 4-dimethylaminopyridine.

Although not absolutely necessary, solvents or diluents mayadvantageously be used for the reaction. Examples that may be mentionedare: halogenated hydrocarbons, especially chlorinated hydrocarbons, suchas tetrachloroethylene, tetrachloroethane, dichloropropane, methylenechloride, dichlorobutane, chloroform, carbon tetrachloride,trichloroethane, trichloroethylene, pentachloroethane,1,2-dichloroethane, 1,1-dichloroethane, 1,2-cis-dichloroethylene,chlorobenzene, fluorobenzene, bromobenzene, dichlorobenzene,dibromobenzene, chlorotoluene, trichlorotoluene; ethers, such as ethylpropyl ether, methyl tert.-butyl ether, n-butyl ethyl ether, di-n-butylether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole,cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether,tetrahydrofuran, dioxane, thioanisole, dichlorodiethyl ether,nitrohydrocarbons, such as nitromethane, nitroethane, nitrobenzene,chloronitrobenzene, o-nitrotoluene; nitriles such as acetonitrile,butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile;aliphatic or cycloaliphatic hydrocarbons, such as heptane, hexane,octane, nonane, cymene, petroleum fractions within a boiling point rangeof from 70° C. to 190° C., cyclohexane, methylcyclohexane, decalin,petroleum ether, ligroin, trimethylpentane, such as2,3,3-trimethylpentane; esters, such as ethyl acetate, acetoacetic acidesters, isobutyl acetate; amides, for example formamide,methylformamide, dimethylformamide; ketones, such as acetone, methylethyl ketone; optionally also water. Mixtures of said solvents anddiluents also come into consideration.

The starting materials of formula II can be obtained in accordance withthe Strecker synthesis by reaction of the aldehyde III with hydrocyanicacid or an alkali cyanide (for example NaCN) in the presence of ammoniaor an ammonium salt: ##STR5##

It is advantageous to use a binary solvent system consisting of, on theone hand, an ether (diethyl ether, dioxane, THF etc.) or an aromatichydrocarbon (benzene, toluene, xylene) and, on the other hand, water andthe operation is performed at from 0° to 100° C.

The starting materials of formula V are obtained by reaction of athioamide of formula VI with an α-halo-β-keto ester of formula VII toform the thiazolyl-5-carboxylic acid ester Va: ##STR6## wherein R' is aC₁ -C₆ hydrocarbon, and then, if desired, conversion into the carboxylicacid V by hydrolysis. The reaction can be carried out in a proticsolvent, such as an alcohol, or in an aprotic solvent, such as benzene,toluene, cyclohexane etc. In some cases it is advisable to add a protonacceptor, such as sodium acetate/acetic acid or a tertiary base (forexample pyridine, triethylamine etc.). The reaction is initially carriedout at temperatures of -60° C. to +40° C. preferably -20° C. to +20° C.The temperature is then increased to +30° C. to +140° C., preferably to+50° C. to +110° C. If, for example, the operation is carried out inbenzene, toluene or cyclohexane, the water that forms can be removedusing a water separator.

In accordance with another process variant, the intermediate of formulaV can also be obtained by first acylating the thioamide of formula VIwith an acid halide of formula VIII to form an N-acylthioamide offormula IX: ##STR7##

The operation is advantageously carried out in an inch solvent, such asacetonitrile or tetrahydrofuran. The proton acceptor used is preferablya tertiary base, such as pyridine, triethylamine,4-dimethylaminopyridine etc.. The reaction should take place in atemperature range of from -40° C. to +80° C., preferably from -20° C. to+20° C. Compound IX is then condensed with a haloester X to form thethiazolyl-5-carboxylic acid ester Va which, if desired, is then convenedinto V in customary manner: ##STR8##

For the cyclisation the N-acylthioamide IX in a protic solvent (forexample a lower alcohol) or aprotic solvent is treated with analcoholate (for example CH₃ --O--Na) or with NaH at temperatures of from-40° C. to +20° C., preferably from -30° C. to 0° C., and then the haloester X is added at from -20° C. to +30° C., preferably from -10° C. to+10° C. The reaction mixture is subsequently heated for several hours atfrom +40° to +120° C., preferably from +60° C. to +100° C., in order toremove the water of reaction.

In the above-mentioned formulae Va to X, R₁ and R₂ are as defined underformula I.

The present invention relates to the described preparation processes,including all subsidiary steps.

The present invention relates also to the novel intermediates of formulaV and their esters with C₁ -C₆ alcohols, especially those wherein R₁ andR₂ are as defined for subgroup Alpha.

Surprisingly, it has now been found that compounds of formula I have,for practical purposes, a very advantageous biocidal spectrum againstphytopathogenic microrganisms, especially against fungi. They have veryadvantageous curative, preventive and, in particular, systemicproperties, and can be used for protecting numerous cultivated plants.With the compounds of formula I it is possible to inhibit or destroy thepests which occur in plants or in pans of plants (fruit, blossoms,leaves, stems, tubers, roots) in different crops of useful plants, whileat the same time the parts of plants which grow later are alsoprotected, for example, from attack by phytopathogenic microorganisms.

Compounds of formula I are effective, for example, against thephytopathogenic fungi belonging to the following classes: Fungiimperfecti (especially Botrytis, also Pyricularia, Helminthosporium,Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (e.g.Rhizoctonia, Hemileia, Puccinia). Furthermore, they are effectiveagainst the class of the Ascomycetes (e.g. Venturia and Erysiphe,Podosphaera, Monilinia, Uncinula), but especially against the Oomycetes(e.g. Phytophthora, Peronospora, Bremia, Pythium, Plasmopara). Thecompounds of formula I can also be used as dressing agents forprotecting seeds (fruit, tubers, grains) and plant cuttings againstfungus infections and against phytopathogenic fungi which occur in thesoil.

The invention relates also to the compositions that contain compounds offormula I as active ingredient, especially plant-protectivecompositions, and to their use in the agricultural sector or relatedfields.

The present invention relates also to the preparation of thosecompositions, which comprises homogeneously mixing the active ingredientwith one or more of the compounds or groups of compounds describedherein. The invention furthermore relates to a method of treatingplants, which comprises applying thereto the novel compounds of formulaI or the novel compositions.

Target crops to be protected within the scope of this invention comprisee.g. the following species of plants: cereals (wheat, barley, rye, oats,rice, maize, sorghum and related crops), beet (sugar beet and fodderbeet), pomes, drupes and soft fruit (apples, pears, plums, peaches,almonds, cherries, strawberries, gooseberries, raspberries andblackberries), leguminous plants (beans, lentils, peas, soybeans), oilplants (rape, mustard, poppy, olives, sunflowers, coconut, castor oilplants, cocoa, groundnuts), cucumber plants (cucumber, marrows, melons),fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons,grapefruit, mandarins), vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae(avocados, cinnamon, camphor), or plants such as tobacco, nuts, coffee,sugar cane, tea, pepper, vines, hops, aubergines, bananas and naturalrubber plants, as well as ornamentals.

The compounds of formula I are normally applied in the form ofcompositions and can be applied to the area or plant to be treated,simultaneously or in succession, with further compounds. These furthercompounds can be fertilisers, micronutrient donors or other preparationsthat influence plant growth. They can also be selective herbicides,insecticides, fungicides, bactericides, nematicides, molluscicides ormixtures of several of these preparations, if desired together withfurther carriers, surfactants or other application-promoting adjuvantscustomarily employed in the art of formulation.

Suitable carriers and adjuvants can be solid or liquid and correspond tothe substances expediently employed in the art of formulation, e.g.natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying a compound of formula I, or anagrochemical composition which contains at least one of said compounds,is foliar application. The number of applications and the rate ofapplication depend on the risk of infestation by the correspondingpathogen. However, the compounds of formula I can also penetrate theplant through the roots via the soil (systemic action) by impregnatingthe locus of the plant with a liquid composition or by applying thecompounds in solid form to the soil, e.g. in granular form (soilapplication). In paddy rice crops, such granulates can be applied inmetered amounts to the flooded rice field. The compounds of formula Imay, however, also be applied to seeds (coating) either by impregnatingthe seeds with a liquid formulation of the active ingredient or bycoating them with a solid formulation. In general, any kind ofpropagation material of a plant may be protected by a compound offormula I, for example the seeds.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation, and are for that purpose advantageously formulated in knownmanner, e.g. into emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions, dilute emulsions, wettable powders,soluble powders, dusts, granulates, and also encapsulations in e.g.polymer substances. As with the nature of the compositions, the methodsof application, such as spraying, atomising, dusting, scattering,coating or pouring, are chosen in accordance with the intendedobjectives and the prevailing circumstances. Advantageous rates ofapplication are normally from 50 g to 5 kg of active ingredient (a.i.)per hectare, preferably from 25 g to 2 kg a.i./ha, most preferably from30 g to 300 g a.i./ha.

The formulations, i.e. the compositions, preparations or mixturescontaining the compound of formula I and, where appropriate, a solid orliquid adjuvant, are prepared in known manner, e.g. by homogeneouslymixing and/or grinding the active ingredients with extenders, e.g.solvents, solid carriers and, where appropriate, surface-activecompounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycol,ethylene glycol monomethyl or monoethyl ether, ketones such ascyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone,dimethyl sulfoxide or dimethylformamide, as well as vegetable oils orepoxidised vegetable oils, such as epoxidised coconut oil or soybeanoil, or water.

The solid carriers used, e.g. for dusts and dispersible powders, arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite.

Especially advantageous application-promoting adjuvants, which canresult in a considerable reduction in the application rate, are natural(animal or vegetable) or synthetic phospholipids of the series of thecephalins and lecithins, which can be obtained, for example, fromsoybeans.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are non-ionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Both so-called water-soluble soaps and water-soluble syntheticsurface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid or ofnatural fatty acid mixtures which can be obtained e.g. from coconut oilor tallow oil. Mention may also be made of fatty acid methyllaurinsalts.

Suitable non-ionic surfactants are polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylenesorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, orbenzyl or hydroxy-lower alkyl radicals.

Further surfactants customarily employed in the art of formulation areknown to the person skilled in the art or can be taken from the relevantspecialist literature.

The anionic, non-ionic or cationic surfactants customarily employed inthe art of formulation are known to the person skilled in the art or canbe taken from the relevant specialist literature:

"McCutcheon's Detergents & Emulsifiers Annual", Mc Publishing Corp.,Glen Rock, N.J., 1988;

M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, ChemicalPublishing Co., N.Y., 1980-1981;

Dr. Helmut Stache, "Tensid-Taschenbuch", Carl Hanser Verlag,Munich/Vienna, 1981.

The agrochemical compositions usually contain 0.1 to 99%, preferably 0.1to 95%, of an active ingredient of formula I, 99.9 to 1%, preferably99.9 to 5%, of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1to 25%, of a surfactant.

Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The compositions may also contain further auxiliaries such asstabilisers, antifoams, viscosity regulators, binders, tackifiers andfertilisers or other active ingredients for obtaining special effects.

The following Examples serve to illustrate the invention but do notlimit the scope thereof.

PREPARATION EXAMPLE 1 a) Preparation of2-methoxymethyl-4-methylthiazole-5-carboxylic acid ethyl ester ##STR9##

20 g of methoxythioacetamide are added, with vigorous stirring, to 31.3g of 2-chloroacetoacetic acid ethyl ester in 400 ml of benzene at roomtemperature and then, using a water separator, heated under reflux for41/2 hours. After cooling to room temperature, the benzenic reactionsolution is diluted with 500 ml of ethyl acetate, washed twice using 80ml of 10% sodium carbonate solution each time and twice using 50 ml ofwater each time, dried over sodium sulfate and filtered. The solventmixture is evaporated off. The yellow oil that remains is crystallisedby trituration with diisopropyl ether. The beige-coloured crystals meltat 36°-37° C.

b) Preparation of 2-methoxymethyl-4-methylthiazole-5-carboxylic acid##STR10##

6.7 g of 85% potassium hydroxide in 1130 ml of ethanol are added at roomtemperature to 22.1 g of 2-methoxymethyl-4-methylthiazole-5-carboxylicacid ethyl ester and the reaction mixture is then heated under refluxfor 18 hours. After cooling, the ethanol is evaporated off and theresidue is dissolved in 200 ml of water. After stirring with activecarbon, the mixture is filtered over Hyflo and the filtrate is acidifiedwith concentrated hydrochloric acid with vigorous stirring. Theresulting yellowish crystals are filtered off, washed with water anddried. After recrystallisation from tetrahydrofuran/petroleum ether(30°-45° C.) (=10:1) the yellowish crystals melt at 168°-169.5° C.

c) Preparation of 2-(2-methoxymethyl-3-methylthiazolyl-5-carbonylamino)-2-(3-thienyl)-acetonitrile ##STR11##

2.38 g of thionyl chloride are added dropwise at 0° C. within a periodof 1/4 hour, with stirring, to 3.5 g ofmethoxymethyl-4-methylthiazole-5-carboxylic acid in 40 ml of pyridine.After stirring for one hour at 0° C., 3.5 g of2-(3-thienyl)-aminoacetonitrile hydrochloride are added and stirring iscontinued for 18 hours while passing nitrogen through the mixture. Afterthe addition, with stirring, of 200 ml of ice-water and 100 ml of ethylacetate, the mixture is acidified with 50 ml of concentratedhydrochloric acid; the organic phase is separated off and extraction iscarried out again with 70 ml of ethyl acetate. The combined extracts arewashed twice using 100 ml of 1N hydrochloric acid each time and oncewith 100 ml of saturated sodium bicarbonate solution, dried over sodiumsulfate and filtered, and the solvent is evaporated off. The yellowishoil that remains is crystallised by trituration with diisopropyl ether.The pale yellow crystals melt at 111°-113° C.

PREPARATION EXAMPLE 2 Preparation of2-(2-methyl-4-cyclopropylthiazolyl-5-carbonylamino)-2-(3-thienyl)acetonitrile##STR12##

8.75 g of 2-(3-thienyl)-aminoacetonitrile hydrochloride are suspended in200 ml of ethyl acetate and, after cooling to +5° C., 12 g oftriethylamine are added, with stirring, within a period of 5 minutes.With vigorous stirring, 10 g of2-methyl-4-cyclopropylthiazole-5-carboxylic acid chloride in 100 ml ofethyl acetate are added dropwise at -5° C. within a period of 1 hour andthe reaction mixture is then stirred for 2 hours at room temperature;100 ml of water are added and the aqueous phase is separated off. Theethyl acetate solution is washed twice using 50 ml of water each time,dried over sodium sulfate and filtered, and the solvent is evaporatedoff. The oil that remains is purified by column chromatography oversilica gel (tetrahydrofuran:hexane=1:1). After the eluant mixture hasbeen evaporated off, the initially brown oil is crystallised bytrituration with petroleum ether (50°-70° C.) and recrystallised fromhexane/dichloromethane. The beige-coloured crystals melt at 108°-110° C.

The following compounds can be prepared in an analogous manner:

                                      TABLE 1                                     __________________________________________________________________________    Compounds of formula                                                           ##STR13##                                                                    Comp. No.                                                                           R.sub.1      R.sub.2  R.sub.3                                                                         Physical constant                               __________________________________________________________________________     1    H            CP.      Q.sub.1                                            2    CH.sub.3     CP.      Q.sub.4                                                                         m.p. 108-110° C.                          3    C.sub.2 H.sub.5                                                                            CP.      Q.sub.3                                                                         m.p. 116-117° C.                          4    H            CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                            5    CP.          CP.      Q.sub.4                                                                         m.p. 93-95° C.                            6    H            CP.      Q.sub.4                                            7    CP.          CH.sub.2 OCH.sub.3                                                                     Q.sub.1                                            8    CH.sub.3     CP.      Q.sub.1                                                                         m.p. 67-68° C.                            9    CH.sub.2 OCH.sub.3                                                                         CP.      Q.sub.4                                                                         m.p. 135-136.5° C.                       10    C.sub.2 H.sub.5                                                                            CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           11    CP.          H        Q.sub.4                                           12    CH.sub.3     CP.      Q.sub.2                                                                         m.p. 91-93° C.                           13                                                                                   ##STR14##   H        Q.sub.4                                           14    CH.sub.2 OCH.sub.3                                                                         H        Q.sub.1                                           15    CP.          CH.sub.3 Q.sub.1                                           16    CP.          CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           17    CH.sub.2 OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           18    CH.sub.3     CP.      Q.sub.3                                                                         m.p. 135-136° C.                         19    C.sub.2 H.sub.5                                                                            CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.1                                           20    cyclobutyl   CH.sub.3 Q.sub.4                                           21    CH.sub.2 OCH.sub.3                                                                         H        Q.sub.4                                           22    CH.sub.3     cyclobutyl                                                                             Q.sub.4                                           23    CH.sub.2 OC.sub.2 H.sub.5                                                                  CP.      Q.sub.4                                           24    CP.          CH.sub.3 Q.sub.4                                                                         m.p. 132-134° C.                         25    C.sub.2 H.sub.5                                                                            CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.4                                           26    CP.          CH.sub.2 OCHF.sub.2                                                                    Q.sub.3                                           27    CH.sub.3     CH.sub.2 OCH.sub.3                                                                     Q.sub.1                                           28    CH.sub.2 OCH.sub.3                                                                         CH.sub.2 OCHF.sub.2                                                                    Q.sub.4                                           29    cyclohexyl   CH.sub.3 Q.sub.4                                           30    CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.2 OCH.sub.3                                                                     Q.sub.1                                           31    CP.          CH.sub.3 Q.sub.2                                           32     CH.sub.3    CH.sub.2 OCH.sub.3                                                                     Q.sub.3                                                                         m.p. 77-81° C.                           33    CP.          CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.1                                           34    C.sub.3 H.sub.7 -n                                                                         CP.      Q.sub.4                                                                         m.p. 114-115° C.                         35    CH.sub.2 OCH.sub.3                                                                         CH.sub.3 Q.sub.1                                                                         m.p. 80-81° C.                           36    CH.sub.2 OC.sub.2 H.sub.5                                                                  H        Q.sub.4                                           37    CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                      CH.sub.3 Q.sub.4                                           38    CH.sub.2 SCH.sub.3                                                                         CH.sub.3 Q.sub.4                                           39    CP.          CH.sub.3 Q.sub.3                                                                         m.p. 127-130° C.                         40    CH.sub.3     CH.sub.2 OCH.sub.3                                                                     Q.sub.2                                           41    CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           42    CP.          CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.4                                           43    CH.sub.2 OCHF.sub.2                                                                        H        Q.sub.4                                           44    C.sub.3 H.sub.7 -n                                                                         CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           45                                                                                   ##STR15##   CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           46                                                                                   ##STR16##   CH.sub.3 Q.sub.4                                           47     CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                     CP.      Q.sub.4                                           48    CH.sub.2 OCH.sub.3                                                                         CH.sub.3 Q.sub.2                                                                         m.p. 79-80° C.                           49    CH.sub.3     CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           50    CH.sub.2 OCH.sub.2 CHCH.sub.2                                                              CH.sub.3 Q.sub.4                                           51                                                                                   ##STR17##   CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           52    CH.sub.2 OCH.sub.2 CF.sub.3                                                                H        Q.sub.4                                           53    CH.sub.3     CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.1                                           54    CH.sub.2 OCH.sub.3                                                                         CH.sub.3 Q.sub.3                                                                         m.p. 96-98° C.                           55    C.sub.3 H.sub.7 -iso                                                                       CP.      Q.sub.4                                                                         m.p. 132-133° C.                         56                                                                                   ##STR18##   CH.sub.3 Q.sub.4                                           57                                                                                   ##STR19##   CP.      Q.sub.4                                           58    CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                      CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           59    CH.sub.3     CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.4                                           60    CH.sub.2 OCH.sub.2C CH                                                                     CH.sub.3 Q.sub.4                                           61                                                                                   ##STR20##   CH.sub.3 Q.sub.4                                           62    CH.sub.2 OCH.sub.2 CF.sub.3                                                                CH.sub.3 Q.sub.4                                           63    CH.sub.2 OCHF.sub.2                                                                        CP.      Q.sub.4                                           64                                                                                   ##STR21##   CH.sub.2 OCH.sub.3                                                                     Q.sub.1                                           65    CP.          C.sub.2 H.sub.5                                                                        Q.sub.1                                           66    CH.sub.3     CH.sub.2 OC.sub.3 H.sub.7 -iso                                                         Q.sub.4                                           67                                                                                   ##STR22##   CH.sub.3 Q.sub.1                                           68    CH.sub.2 OCH.sub.3                                                                         CH.sub.3 Q.sub.4                                                                         m.p. 111-113° C.                         69                                                                                   ##STR23##   CH.sub.3 Q.sub.4                                           70    CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.3 Q.sub.1                                           71                                                                                   ##STR24##   CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           72    CH.sub.2 OCHF.sub.2                                                                        CH.sub.2 OCH.sub.3                                                                     Q.sub.1                                           73    CH.sub.3     CH.sub.2 OCHF.sub.2                                                                    Q.sub.1                                           74                                                                                   ##STR25##   CH.sub.3 Q.sub.3                                           75    C.sub.3 H.sub.7 -iso                                                                       CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.4                                           76                                                                                   ##STR26##   CH.sub.3 Q.sub.4                                           77    CP.          C.sub.2 H.sub.5                                                                        Q.sub.4                                                                         m.p. 116-117.5° C.                       78    C.sub.2 H.sub.5                                                                            CP.      Q.sub.2                                                                         m.p. 84-86° C.                           79    CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.3 Q.sub.2                                           80                                                                                   ##STR27##   CH.sub.3 Q.sub.2                                           81    C.sub.4 H.sub.9 -n                                                                         CP.      Q.sub.1                                           82                                                                                   ##STR28##   CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.1                                           83    CH.sub.3     CH.sub.2 OCHF.sub.2                                                                    Q.sub.4                                           84    CH.sub.2 OCHF.sub.2                                                                        CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           85                                                                                   ##STR29##   CH.sub.3 Q.sub.4                                           86    CP.          CP.      Q.sub.1                                                                         m.p. 86-88° C.                           87                                                                                   ##STR30##   CH.sub. 3                                                                              Q.sub.4                                           88    CH.sub.3     CH.sub.2 OCH.sub.2 CF.sub.3                                                            Q.sub.4                                           89    CH.sub.2 OCH.sub.2 CF.sub.3                                                                CP.      Q.sub.4                                           90    C.sub.2 H.sub.5                                                                            CP.      Q.sub.4                                                                         m.p. 81-83° C.                           91                                                                                   ##STR31##   CH.sub.2 OC.sub.2 H.sub.5                                                              Q.sub.4                                           92    C.sub.4 H.sub.9 -n                                                                         CP.      Q.sub.4                                           93    CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.3 Q.sub.3                                                                         n.sub.D.sup.25 1.5723                           94    C.sub.2 H.sub.5                                                                            CP.      Q.sub.1                                                                         m.p. 73-75° C.                           95    CH.sub.2 OCH.sub.3                                                                         CP.      Q.sub.1                                                                         m.p. 81-83° C.                           96    CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.3 Q.sub.4                                           97    C.sub.2 H.sub.5                                                                            CH.sub.2 OCH.sub.3                                                                     Q.sub.1                                           98    CH.sub.2 OCHF.sub.2                                                                        CH.sub.3 Q.sub.1                                           99    CH.sub.2 OCH.sub.2 CF.sub.3                                                                CH.sub.2 OCH.sub.3                                                                     Q.sub.4                                           100                                                                                  ##STR32##   C.sub.2 H.sub.5                                                                        Q.sub.4                                           101   CH.sub.2 OCHF.sub.2                                                                        C.sub.2 H.sub.5                                                                        Q.sub.4                                           102                                                                                  ##STR33##   CH.sub.3 Q.sub.4                                           103   CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                      CH.sub.3 Q.sub.1                                           104   CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                        Q.sub.4                                                                         m.p. 111-112° C.                         105   CH.sub.2 OCHF.sub.2                                                                        CH.sub.3 Q.sub.4                                           106   CH.sub.2 OCH.sub.2 CF.sub.3                                                                C.sub.2 H.sub.5                                                                        Q.sub.4                                           107   CP.          C.sub.3 H.sub.7 -iso                                                                   Q.sub.4                                                                         m.p. 108-111° C.                         108   CH.sub.2 OCHF.sub.2                                                                        C.sub.3 H.sub.7 -iso                                                                   Q.sub.1                                           109   CH.sub.2 OC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                        Q.sub.1                                           110   CH.sub.2 OCHF.sub.2                                                                        CH.sub.3 Q.sub.2                                                                         oil                                             111   CH.sub.2 OC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                        Q.sub.4                                                                         m.p. 126-129° C.                         112                                                                                  ##STR34##   C.sub.3 H.sub.7 -n                                                                     Q.sub.4                                           113   CH.sub.2 OCH.sub.3                                                                         C.sub. 3 H.sub.7 -iso                                                                  Q.sub.4                                           114   CH.sub.2 OCHF.sub.2                                                                        C.sub.3 H.sub.7 -iso                                                                   Q.sub.4                                           115   CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                      C.sub.2 H.sub.5                                                                        Q.sub.4                                           116   CH.sub.2 OC.sub.2 H.sub.5                                                                  C.sub.3 H.sub.7 -iso                                                                   Q.sub.4                                           117   CH.sub.2 OCH.sub.2 CF.sub.3                                                                CH.sub.3 Q.sub.1                                           118   CH.sub.2 OC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                        Q.sub.3                                                                         m.p. 96-97° C.                           119   CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                        Q.sub.3                                                                         m.p. 78-83° C.                           120   CP.          C.sub.2 H.sub.5                                                                        Q.sub.3                                                                         m.p. 106-109° C.                         121   CH.sub.2 OCH.sub.3                                                                         CP.      Q.sub.3                                                                         m.p. 104-106° C.                         122   CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                        Q.sub.2                                                                         m.p. 81-83° C.                           123   CH.sub.2 OCH.sub.3                                                                         CP.      Q.sub.2                                                                         m.p. 105-106° C.                         124   CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                        Q.sub.1                                                                         m.p. 104-105° C.                         125   C.sub.3 H.sub.7 iso                                                                        CP.      Q.sub.1                                                                         m.p. 89-92° C.                           126   C.sub.3 H.sub.7 iso                                                                        CP.      Q.sub.3                                                                         m.p. 129-131° C.                         127   C.sub.3 H.sub.7 iso                                                                        CP.      Q.sub.2                                                                         m.p. 109-110° C.                         128   C.sub.3 H.sub.7 n                                                                          CP.      Q.sub.1                                                                         m.p. 86-87° C.                           129   C.sub.3 H.sub.7 n                                                                          CP.      Q.sub.3                                                                         m.p. 74-76° C.                           130   C.sub.3 H.sub.7 n                                                                          CP.      Q.sub.2                                                                         m.p. 81-83° C.                           131   CH.sub.2 OCHF.sub.2                                                                        CH.sub.3 Q.sub.3                                           132   CH.sub.2 OCHF.sub.2                                                                        C.sub.2 H.sub.5                                                                        Q.sub.1                                           133   CH.sub.2 OCHF.sub.2                                                                        C.sub.2 H.sub.5                                                                        Q.sub.2                                           134   CH.sub.2 OCHF.sub.2                                                                        C.sub.2 H.sub.5                                                                        Q.sub.3                                           135   CH.sub.2 OCHF.sub.2                                                                        CP.      Q.sub.1                                           136   CH.sub.2 OCHF.sub.2                                                                        CP.      Q.sub.2                                           137   CH.sub.2 OCHF.sub.2                                                                        CP.      Q.sub.3                                           138   CP.          CP.      Q.sub.2                                                                         m.p. 103-105° C.                         139   CP.          CP.      Q.sub.3                                                                         m.p. 123-126° C.                         140   CP.          C.sub.3 H.sub.7 -n                                                                     Q.sub.1                                                                         m.p. 106-108° C.                         141   CP.          C.sub.3 H.sub.7 iso                                                                    Q.sub.2                                                                         m.p. 108-110° C.                         142   CP.          C.sub.3 H.sub.7 iso                                                                    Q.sub.1                                                                         m.p. 97-100° C.                          143   CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 iso                                                                    Q.sub.3                                                                         m.p. 89-91° C.                           144   CP.          C.sub.3 H.sub.7 -n                                                                     Q.sub.2                                                                         m.p. 111-114° C.                         145   CP.          C.sub.3 H.sub.7 iso                                                                    Q.sub.3                                                                         m.p. 101-103° C.                         146   CH.sub.2 OC.sub.2 H.sub.5                                                                  CP.      Q.sub.1                                                                         m.p. 116-118° C.                         147   CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 -n                                                                     Q.sub.3                                                                         m.p. 98-101° C.                          148   CH.sub.2 OC.sub.2 H.sub.5                                                                  CP.      Q.sub.3                                                                         m.p. 123-125° C.                         149   CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 iso                                                                    Q.sub.1                                                                         m.p. 87-90° C.                           150   CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 -n                                                                     Q.sub.1                                                                         m.p. 91-94° C.                           151   CP.          C.sub.3 H.sub.7 -n                                                                     Q.sub.3                                                                         m.p. 103-106°  C.                        152   CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 -n                                                                     Q.sub.2                                                                         m.p. 85-87° C.                           153   CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 iso                                                                    Q.sub.2                                                                         m.p. 93-95° C.                           154   CP.          C.sub.3 H.sub.7 -n                                                                     Q.sub.4                                                                         m.p. 114-120° C.                         155   CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 -n                                                                     Q.sub.4                                                                         m.p. 124-126° C.                         156   CH.sub.2 OC.sub.2 H.sub.5                                                                  CP.      Q.sub.2                                                                         m.p. 109-111° C.                         __________________________________________________________________________     Q.sub.1 = 2-furanyl                                                           Q.sub.2 = 3-furanyl                                                           Q.sub.3 = 2-thienyl                                                           Q.sub.4 = 3-thienyl                                                           CP. = cyclopropyl                                                        

                  TABLE 2                                                         ______________________________________                                        Intermediates of formula V                                                     ##STR35##                                                                    Comp. No.                                                                             R.sub.1      R.sub.2   Physical constant                              ______________________________________                                        2.1     CP.          CH.sub.3  m.p. 198-200° C.                        2.2     CP.          C.sub.2 H.sub.5                                                                         m.p. 96-97° C.                          2.3     CP.          C.sub.3 H.sub.7 -n                                                                      m.p. 104-106° C.                        2.4     CP.          C.sub.3 H.sub.7 -iso                                                                    m.p. 84-87° C.                          2.5     CH.sub.3     CP.       m.p. 190-191° C.                        2.6     C.sub.2 H.sub.5                                                                            CP.       m.p. 158-159° C.                        2.7     C.sub.3 H.sub.7 -iso                                                                       CP.       m.p. 122-123° C.                        2.8     C.sub.3 H.sub.7 -n                                                                         CP.       m.p. 161-162° C.                        2.9     CH.sub.2 OCH.sub.3                                                                         CH.sub.3  m.p. 168-169.5° C.                      2.10    CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                         m.p. 146-147° C.                        2.11    CH.sub.2 OCH.sub.3                                                                         CP.       m.p. 159-161° C.                        2.12    CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub. 3 m.p. 185-186° C.                        2.13    CH.sub.2 OC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                         m.p. 114-115° C.                        2.14    CH.sub.2 OC.sub.2 H.sub.5                                                                  CP.       m.p. 132-134° C.                        2.15    CP.          CP.       m.p. 102-104° C.                        2.16    CH.sub.2 OCHF.sub.2                                                                        CH.sub.3                                                 2.17    CH.sub.2 OCHF.sub.2                                                                        C.sub.2 H.sub.5                                          2.18    CH.sub.2 OCHF.sub.2                                                                        CP.                                                      2.19    CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 -n                                                                      m.p. 137-139° C.                        2.20    CH.sub.2 OCH.sub.3                                                                         C.sub.3 H.sub.7 -iso                                                                    m.p. 148-151° C.                        ______________________________________                                         CP. = cyclopropyl                                                        

In the presence of an acid catalyst, such as HCl, it is readily possibleto obtain the corresponding carboxylic acid C₁ -C₆ alkyl esters from theacids of Table 2 by esterification with methanol, ethanol or one of theisomeric alcohols propanol, pentanol and hexanol.

2.Formulation Examples for active ingredients of formula I (throughoutpercentages are by weight)

    ______________________________________                                        2.1. Wettable powder a)      b)      c)                                       ______________________________________                                        a compound of Table 1                                                                              25%     50%     75%                                      sodium lignosulfonate                                                                               5%      5%     --                                       sodium laurylsulfate  3%     --       5%                                      sodium diisobutylnaphthalenesulfonate                                                              --       6%     10%                                      octylphenol polyethylene glycol ether                                                              --       2%     --                                       (7-8 moles of ethylene oxide)                                                 highly dispersed silicic acid                                                                       5%     10%     10%                                      kaolin               62%     27%     --                                       ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        2.2. Emulsifiable concentrate                                                 ______________________________________                                        a compound of Table 1  10%                                                    octylphenol polyethylene glycol ether                                                                 3%                                                    (4-5 moles of ethylene oxide)                                                 calcium dodecylbenzenesulfonate                                                                       3%                                                    cyclohexanone          34%                                                    xylene mixture         50%                                                    ______________________________________                                    

Emulsions of any required concentration can be produced from thisconcentrate by dilution with water.

    ______________________________________                                        2.3. Dusts           a)     b)                                                ______________________________________                                        a compound of Table 1                                                                               5%     8%                                               talcum               95%    --                                                kaolin               --     92%                                               ______________________________________                                    

Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier, and grinding the mixture in a suitable mill.

    ______________________________________                                        2.4. Extruder granulate                                                       ______________________________________                                        a compound of Table 1                                                                            10%                                                        sodium lignosulfonate                                                                             2%                                                        carboxymethylcellulose                                                                            1%                                                        kaolin             87%                                                        ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded andsubsequently dried in a stream of air.

    ______________________________________                                        2.5. Coated granulate                                                         ______________________________________                                        a compound of Table 1 3%                                                      polyethylene glycol (mol. wt. 200)                                                                  3%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        2.6. Suspension concentrate                                                   ______________________________________                                        a compound of Table 1   40%                                                   ethylene glycol         10%                                                   nonylphenol polyethylene glycol ether                                                                  6%                                                   (15 moles of ethylene oxide)                                                  sodium lignosulfonate   10%                                                   carboxymethylcellulose   1%                                                   37% aqueous formaldehyde solution                                                                     0.2%                                                  silicone oil in the form of a 75%                                             aqueous emulsion        0.8%                                                  water                   32%                                                   ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

3. Biological Examples I. Action against Phytophthora infestans ontomato plants

a) Curative Action

After a cultivation period of 3 weeks, tomato plants of the "Roter Gnom"variety are sprayed with a zoospore suspension of the fungus andincubated in a cabinet at 18° to 20° and saturated humidity. Thehumidification is discontinued after 24 hours. When the plants havedried, they are sprayed with a mixture containing a wettable powderformulation of the test compound in a concentration of 600, 200 or 60ppm. When the spray-coating has dried, the plants are returned to thehumidity cabinet for four days. The effectiveness of the test compoundsis evaluated on the basis of the number and size of the typical leafspecks occurring after that time.

b) Preventive Systemic Action

A wettable powder formulation of the test compound is applied in aconcentration of 60 ppm (based on the volume of the soil) to the surfaceof the soil of three-week-old tomato plants of the "Roter Gnom" varietyin pots. After three days the underside of the leaves of the plants aresprayed with a zoospore suspension of Phytophthora infestans. The plantsare then kept in a spraying cabinet at 18° to 20° C. and saturatedhumidity for 5 days. The effectiveness of the test compounds isevaluated on the basis of the number and size of the typical leaf specksthat form after that time.

The following compounds of Table 1 inhibit disease attack to less than10%: Nos. 2, 3, 5, 8, 9, 12, 18, 24, 32, 34, 35, 39, 48, 54, 55, 63, 68,77, 78, 90, 93, 95, 98, 104, 107, 110, 111, 113, 116, 118 to 130 and 138to 156.

II. Action against Plasmopara viticola (Bert.et Curt.) (Berl et DeToni)on vines

a) Residual Preventive Action

Vine cuttings of the "Chasselas" variety are raised in a greenhouse. Inthe 10-leaf stage, 3 plants are sprayed with a mixture prepared from awettable powder formulation of the test compound (200 ppm of activeingredient). After the spray-coating has dried, the undersides of theleaves of the plants are uniformly infected with a spore suspension ofthe fungus. The plants are then kept in a humidity chamber for 8 days.After this time the control plants exhibit clear symptoms of disease.The effectiveness of the test compounds is evaluated on the basis of thenumber and size of the infection sites on the treated plants.

b) Curative action

Vine cuttings of the "Chasselas" variety are raised in a greenhouse andin the 10-leaf stage the undersides of the leaves are infected with aspore suspension of Plasmopara viticola. After 24 hours in a humiditychamber the plants are sprayed with an active ingredient mixtureprepared from a wettable powder formulation of the test compound (500ppm of active ingredient). The plants are then kept in the humiditycabinet for a further 7 days. After this time the control plants exhibitclear symptoms of disease. The effectiveness of the test compounds isevaluated on the basis of the number and size of the infection sites onthe treated plants.

In this test too, all the compounds mentioned in Example 1 inhibitdisease attack to less than 10%.

III. Action against Pythium debaryanum on sugar beet (Beta vulgaris)

a) Action after Soil Application

The fungus is cultured on sterile oat grains and added to a soil/sandmixture. The infected soil is introduced into pots and sown with sugarbeet seeds. Immediately after sowing, wettable powder formulations ofthe test compounds in the form of aqueous suspensions are poured ontothe soil (20 ppm of active ingredient, based on the volume of the soil).The pots are then placed in a greenhouse at 20°-b 24° C. for 2-3 weeks.The soil is kept constantly uniformly wet by lightly spraying withwater. The test is evaluated by determining the emergence rate of thesugar beet plants and the proportion of healthy and diseased plants.

b) Action after Dressing

The fungus is cultured on sterile oat grains and added to a soil/sandmixture. The infected soil is introduced into pots and sown with sugarbeet seeds that have been dressed with a dressing powder formulation ofthe test compounds (1000 ppm of active ingredient, based on the weightof the seeds). The pots are placed in a greenhouse at 20°-24° C. for 2-3weeks. The soil is kept uniformly wet by lightly spraying with water.The test is evaluated by determining the emergence rate of the sugarbeet plants and the proportion of healthy and diseased plants.

An emergence rate of more than 80% is obtained with compounds ofTable 1. The corresponding control plants exhibit an emergence rate ofless than 30% and have an unhealthy appearance.

I claim:
 1. Thiazolyl-5-carbonamide derivatives of formula I and acidaddition salts and metal salt complexes thereof ##STR36## wherein R₃ is2-furanyl, 2-thienyl, 3-furanyl or 3-thienyl; and whereinR₁ and R₂ eachindependently of the other have the following meanings:a) C₃ -C₆cycloalkyl that is unsubstituted or substituted by methyl or methylthio,b) the group --CH₂ --X--R₄, and c) one of the two substituents R₁ and R₂may also be hydrogen or C₁ -C₄ alkyl, wherein X is oxygen or sulfur, andR₄ is C₁ -C₄ alkyl that may be unsubstituted or substituted by halogenor, in the case of C₂ -C₄ alkyl, also by C₁ -C₃ alkoxy, or wherein R₄ isC₃ -C₄ alkenyl, C₃ -C₄ alkynyl or a phenyl group or benzyl group ofwhich the aromatic ring is unsubstituted or may be substituted byhalogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, CF₃ or by NO₂.
 2. Compounds offormula I according to claim 1, wherein one of the two substituents R₁and R₂ is C₃ -C₆ cycloalkyl that is unsubstituted or substituted bymethyl or methylthio, and the other substituent isd) cyclobutyl,cyclopropyl, methylcyclopropyl or methylthiocyclopropyl, e) the group--CH₂ --X--R₄ or f) hydrogen or C₁ -C₄ alkyl, while R₃, X and R₄ are asdefined above.
 3. Compounds of formula I according to claim 2, whereinone of the two substituents R₁ and R₂ is C₃ -C₆ cycloalkyl and the otheris cyclobutyl or cyclopropyl, while R₃ is as defined above.
 4. Compoundsof formula I according to claim 3, wherein R₁ and R₂ are cyclopropyl. 5.Compounds of formula I according to claim 2, whereinR₁ is hydrogen, C₁-C₄ alkyl or the group --CH₂ --X--R₄, X is oxygen or sulfur, and R₄ isC₁ -C₄ alkyl that is unsubstituted or substituted by fluorine or, in thecase of C₂ -C₄ alkyl, may also be substituted by C₁ -C₃ alkoxy; orwherein R₄ is allyl, propargyl, phenyl or benzyl, the aromatic rings ofthe latter radicals being unsubstituted or substituted by one or two ofthe substituents fluorine, chlorine, methyl, ethyl, methoxy and CF₃,while R₂ is C₃ -C₆ cycloalkyl that is unsubstituted or substituted bymethyl or methylthio, while R₃ is as defined above.
 6. Compoundsaccording to claim 5, whereinR₁ is hydrogen, C₁ -C₄ alkyl or --CH₂--O--R₄, R₂ is cyclobutyl, cyclopropyl, methylcyclopropyl ormethylthiocyclopropyl, and R₄ is C₁ -C₄ alkyl that is unsubstituted orfluoro-substituted or, in the case of C₂ -C₄ alkyl, may also besubstituted by methoxy or ethoxy; or wherein R₄ is allyl, propargyl,phenyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl orfluorobenzyl, while R₃ is as defined above.
 7. Compounds according toclaim 6, whereinR₂ is cyclopropyl, and R₄ is methyl, ethyl,fluoromethyl, difluoromethyl, trifluoroethyl, allyl, propargyl, phenylor benzyl.
 8. Compounds according to claim 7, wherein R₁ is hydrogen, C₁-C₃ alkyl, methoxymethyl or ethoxymethyl.
 9. Compounds of formula Iaccording to claim 1, wherein eithera) R₁ is CH₃, C₂ H₅, n-propyl, isoC₃H₇, CH₂ --O--CH₃, CH₂ --O--C₂ H₅, CH₂ --O--CHF₂ or cyclopropyl, andR₂ iscyclopropyl, or wherein b) R₁ is CH₂ --O--CH₃, CH₂ --O--C₂ H₅, CH₂--O--CHF₂ or cyclopropyl andR₂ is CFC₃ -alkyl, and R₃ is as definedabove.
 10. Compounds of formula I according to claim 9, wherein R₁ ismethyl, ethyl, n-propyl or isopropyl and R₂ is cyclopropyl. 11.Compounds of formula I according to claim 9, whereinR₁ is CH₂ --O--CH₃,CH₂ --O--C₂ H₅ or cyclopropyl and R₂ is methyl, ethyl, n-propyl,isopropyl or cyclopropyl.
 12. A microbicidal composition for the controlof plant diseases containing as active ingredient a compound of formulaI together with a suitable carrier therefor.
 13. A method of controllingplant diseases or preventing attack by disease, which comprises theapplication of a compound of formula I to the plants, to their growingsite, to parts of the plants or to plant propagation material.